US6221430B1 - Process for making a detergent particle - Google Patents

Process for making a detergent particle Download PDF

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US6221430B1
US6221430B1 US08/625,445 US62544596A US6221430B1 US 6221430 B1 US6221430 B1 US 6221430B1 US 62544596 A US62544596 A US 62544596A US 6221430 B1 US6221430 B1 US 6221430B1
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acid
weight
particle
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Michael Frederick Tompsett
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments

Definitions

  • the present invention relates to a process for applying a full or partial coating to particles of hygroscopic material, and to detergent compositions adapted for use in machine dishwashing containing such coated particles.
  • compositions designed for use in automatic dishwasher machines are well known, and a consistent effort has been made by detergent manufacturers to improve the cleaning and/or rinsing efficiency of said compositions on chinaware, glassware and silverware, as reflected by numerous patent publications.
  • speckle particles are based on enzyme-containing prills to which coloured dyestuffs have been applied.
  • This has the disadvantage to the formulator of a detergent product that the amount of speckle, and hence colour in the product is related to the in-product level of the enzyme component whose stain removal performance is highly sensitive to its level of inclusion. Varying the level of the enzyme to achieve the desirable level of speckle effect in product can thus have a major impact on the peformance of the detergent product.
  • the formulator faces a problem that such substrate should have no negative effect on the detergent performance of the product, and preferably should contribute to the detergency performance.
  • the fomulator is also faced with the problem that the speckle should have good abrasion colour stability, that is good resistance to dye abrasion (e.g. in any further packaging/processing steps). Similarly, the colour of the speckle should be resistant to being washed off in any further processing steps involving liquid application, e.g. by spraying-on, steps.
  • the speckle furthermore should possess good in-product colour storage stability including resistance to oxidation and other processes which may cause degradation of the dyestuff.
  • weight ratio of hygroscopic material to organic binder in the finished particle is from 1000:1 to 10:1, expressed on a dry weight basis.
  • sodium silicate providing at least 5% by weight of the total SiO 2 to the composition is in the form of the coated silicate particles according to the process aspect of the invention.
  • the pH of a 1% solution of the detergent composition measured at 20° C. is preferably from 9.0 to 11.5.
  • the process according to the present invention provides a method of applying a coating to a base particle.
  • the process comprises the essential steps of
  • the hygroscopic nature of the material is important to the working of the process in that when the aqueous mixture of the binder, and optionally the dyestuff, are sprayed onto the base particle its hygroscopic nature tends to draw the water into the particle, thus leaving a relatively even ‘coating’ of binder and dyestuff on the surface of the particle.
  • particularly suitable hygroscopic materials are those having structures with a relatively small pore size, especially those having a pore size of less than 15 ⁇ m.
  • Suitable hygroscopic materials include certain clays, aluminosilicates, silica and crystalline layered silicates.
  • the aqueous mixture to be sprayed onto the base particle contains, in an essential aspect, an organic binder.
  • the weight ratio of hygroscopic material to organic binder in the finished particle is from 1000:1 to 10:1 preferably from 500:1 to 50:1, expressed on a dry weight basis.
  • suitable organic binders include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • Preferred examples of such compounds are the polymers which contain acrylic acid, that is to say homopolymers of acrylic acid and copolymers with any suitable other monomer units, and which have a average molecular weight of from 2,000 to 100,000.
  • Suitable other monomer units include modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a average molecular weight of from 20,000 to 100,000.
  • Preferred acrylic acid containing polymers have an average molecular weight of less than 15,000, and include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.
  • acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula —[CR 2 —CR 1 (CO—O—R 3 )]— wherein at least one of the substituents R 1 , R 2 or R 3 , preferably R 1 or R 2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R 1 or R 2 can be a hydrogen and R 3 can be a hydrogen or alkali metal salt.
  • the most preferred copolymer of this type has a average molecular weight of from 4500 to 3000 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.
  • polyamino compounds are useful as organic binders herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Suitable binders include the C 10 -C 20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C 15 -C 20 primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymeric materials.
  • Polyvinylpyrrolidones with an average average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average average molecular weight of from 600 to 5 ⁇ 10 6 preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents.
  • polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C 10 -C 20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C 10 -C 20 alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole.
  • binders include the C 10 -C 20 mono- and diglycerol ethers and also the C 10 -C 20 fatty acids.
  • the aqueous mixture containing the organic binder also contains a dyestuff.
  • the weight ratio of hygroscopic material to dyestuff, where present, in the finished particle is from 1000:1 to 50:1, preferably from 500:1 to 100:1 expressed on a dry weight basis.
  • the dyestuff can be any suitable dyestuff, particularly organic based dyestuffs which have found common usage in the preparation of coloured ‘speckle’ particles for inclusion in detergent products.
  • suitable dyestuffs include E104—food yellow 13 (quinoline yellow), E110—food yellow 3 (sunset yellow FCF), E131—food blue 5 (patent blue V), E133—food blue 2 (brilliant blue FCF), E140—natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine).
  • the process according to the present invention involves treating a base particle to provide a partially or fully coated ‘finished’ particle.
  • the process includes two steps namely a spraying-on step and a drying step. These may be carried out in stepwise fashion, or alternatively both steps may occur simultaneously.
  • the spraying-on step comprises spraying an aqueous mixture comprising organic binder and optionally a dyestuff onto the base particle.
  • This spraying-on can be achieved by any spraying process commonly known to the person skilled in the art.
  • the spraying-on step is preferably carried out slowly to allow the base granule to adsorp the mixture, and absorb the water part of the aqueous mixture.
  • the spraying-on is carried out whilst the particles are agitated by some means.
  • Suitable agitation means comprise drum mixers, KM Loedige (tradename) mixers, V blenders, spray granulators, fluidised beds, turbodisers (tradename) and Schugi (tradename) mixers.
  • the drying step involves drying the particles obtained from the first step. This drying process may be carried out using any known drying apparatus such as fluidised bed driers and granulator driers.
  • the spraying-on and drying steps occur simultaneously, most preferably being carried out as a continuous process in a fluidised bed drier.
  • the finished particles preferably have a moisture content of from 0.5% to 15%, preferably from 5% to 10%, by weight of the finished particle.
  • compositions which are particularly adapted for use in a machine dishwashing method.
  • Such compositions are formulated to enable the removal of, typically food based, soils and stains from soiled tableware under the conditions present in a machine dishwasher.
  • the compositions are low foaming, preferably containing only low levels of low-foaming surfactants.
  • the detergent composition contains
  • an alkalinity system comprising sodium silicate having an SiO 2 :Na 2 O ratio of from 1.0 to 3.0 present at a level of from 0.5% to 20% SiO 2 by weight of the composition.
  • the sodium silicate is preferably present in the composition at a level of from 2% to 15%, most preferably from 3% to 12% by weight of SiO 2 .
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • the alkalinity system preferably contains only sodium silicate having an SiO 2 :Na 2 O ratio of from 1.6 to 3.0, preferably from 1.6 to 2.4, most preferably 2.0.
  • the alkalinity system also contains sodium metasilicate, present at a level of at least 0.4% SiO 2 by weight.
  • Sodium metasilicate has a nominal SiO 2 :Na 2 O ratio of 1.0.
  • the weight ratio of said sodium silicate to said sodium metasilicate, measured as SiO 2 is then from 50:1 to 5:4, preferably from 20:1 to 3:2, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromelitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures a re also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50° C., especially less than about 40° C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on Nov. 15, 1973.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • the present compositions have a pH measured as a 1% solution in distilled water at 20° C. of from 9.0 to 11.5, preferably from 9.5 to 11.2, most preferably from 10.0 to 11.0.
  • compositions of the invention may be formulated as detergent compositions comprising additional detergent ingredients, preferably selected from oxygen bleachinmg systems, surfactants, heavy metal ion sequestrants, crystal growth inhibitors, enzymes, organic polymeric compounds, corrosion inhibitors, and suds suppressors.
  • additional detergent ingredients preferably selected from oxygen bleachinmg systems, surfactants, heavy metal ion sequestrants, crystal growth inhibitors, enzymes, organic polymeric compounds, corrosion inhibitors, and suds suppressors.
  • a preferred component of the compositions in accord with the invention is an oxygen-releasing bleaching system.
  • the bleaching system comprises a hydrogen peroxide source and a peroxyacid bleach precursor compound.
  • the production of the peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Suitable sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • compositions preferably include a hydrogen peroxide source, as an oxygen-releasing bleach.
  • Suitable hydrogen peroxide sources include the inorganic perhydrate salts.
  • the inorganic perhydrate salts are normally incorporated in the form of the sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Sodium perborate can be in the form of the monohydrate of nominal formula NaBO 2 H 2 O 2 or the tetrahydrate NaBO 2 H 2 O 2 .3H 2 O.
  • Sodium percarbonate which is a preferred perhydrate for inclusion in compositions in accordance with the invention, is an addition compound having a formula typically corresponding to 2Na 2 CO 3 .3H 2 O 2 , and is available commercially as a crystalline solid.
  • the percarbonate is most preferably incorporated into such compositions in a coated form which provides in product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate.
  • mixed salt of a water soluble alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 200 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na 2 SO 4 .n.Na 2 CO 3 wherein n is form 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable, and preferred, coating material contains sodium silicate having an SiO 2 :Na 2 O of from 1.6 to 3.0 and/or sodium metasilicate.
  • sodium silicate and/or sodium metasilicate can perform three functions, namely: enhancing storage stability of the perhydrate salt, delaying dissolution of the perhydrate salt and hence release of hydrogen peroxide to the wash solution, and providing SiO 2 to the wash solution as part of the alkalinity system in accord with the invention.
  • coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • Peroxyacid bleach precursors are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the compositions.
  • Suitable peroxyacid bleach precursors typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • Suitable peroxyacid bleach precursor compounds include the N-acylated lactams, perbenzoic acid and perbenzoic acid derivative precurosrs, peroxyacid precursors and alkyl fatty acid precursor compounds described in more detail hereinafter.
  • N-acylated precursor compounds of the lactam class are disclosed generally in GB-A-855735. Whilst the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams.
  • Suitable N-acylated lactam precursors have the formula:
  • n is from 0 to about 8, preferably from 0 to 2
  • R 6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms
  • Suitable caprolactam bleach precursors are of the formula:
  • R 1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most preferably R 1 is phenyl.
  • Suitable valero lactams have the formula:
  • R 1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
  • R 1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
  • the most preferred materials are those which are normally solid at ⁇ 30° C., particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkoxy derivatives.
  • Precursor compounds wherein R 1 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains.
  • Mixtures of ‘hydrophobic’ and ‘hydrophilic’ caprolactams and valero lactams, typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain removal benefits.
  • caprolactam and valerolactam precursors include benzoyl caprolactam, nonanoyl capro-lactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, (6-octanamidocaproyl)oxybenzene-sulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)-oxybenzenesulfonate, and mixtures thereof.
  • Examples of highly preferred substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, ethoxybenzo
  • any perbenzoic acid precursors are suitable herein, including those of the N-acylated lactam class, which are preferred.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
  • Preferred perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
  • Suitable perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the perbenzoic group is substituted by essentially any functional group including alkyl groups.
  • Another preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • R 1 is an aryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl.
  • R 1 and R 5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • pKa of the conjugate acid of the leaving group although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behaviour are those in which their conjugate acid has a pKa in the range of from 4 to 13, preferably from 6 to 11 and most preferably from 8 to
  • Preferred bleach precursors are those wherein R 1 , R 2 and R 5 are as defined for the amide substituted compounds and L is selected from the group consisting of:
  • R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • Y is H or a solubilizing group.
  • the preferred solubilizing groups are —SO 3 ⁇ M + , —CO 2 ⁇ M + , —SO 4 ⁇ M + , —N + (R 3 ) 4 X ⁇ and O ⁇ —N(R 3 ) 3 and most preferably —SO 3 ⁇ M + and —CO 2 ⁇ M wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • bleach activators with a leaving group that does not contain a solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
  • Cationic peroxyacid precursor compounds are also suitable herein.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part with an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are described in U.S. Pat. Nos. 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,3,3-tri-methyl hexanoyloxybenzene sulfonate.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis.
  • Preferred precursors of this type give rise to peracetic acid on perhydrolysis.
  • Preferred alkyl fatty peroxyacid precursor compounds of the imide type include the N-,N,N 1 N 1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • peroxyacid bleach activator compounds are the amide substituted compounds of the following general formulae:
  • R 1 is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl.
  • R 1 and R 5 should not contain more than 18 carbon atoms in total.
  • L may be selected from any of the leaving groups described hereinbefore for the analogues having R 1 as an aryl or alkaryl group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • compositions may also contain, as oxygen-releasing bleaches, organic peroxyacids, typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • R 1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl.
  • R 1 and R 5 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diperoxydodecanedioc acid, diperoxytetra decanedioc acid, diperoxyhexadecanedioc acid, mono- and diperazelaic acid, mono- and diperbrassylic acid, monoperoxy phthalic acid and its magnesium salt, perbenzoic acid, and their salts as disclosed in, for example, EP-A-0341 947.
  • compositions of the present invention may less preferably contain a partially soluble or insoluble builder compound.
  • partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043.
  • largely water insoluble builders include the sodium aluminosilicates, including Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP, Zeolite HS and mixtures thereof.
  • a highly preferred component of the compositions of the invention is a surfactant system comprising surfactant selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • the surfactant system comprises low foaming surfactant, which is typically nonionic in character.
  • the surfactant system is typically present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of the compositions.
  • nonionic surfactants useful for detersive purposes can be included in the compositions.
  • Preferred, non-limiting classes of useful nonionic surfactants are listed below.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the C 10 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C 12 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a average molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a average molecular weight of from about 2500 to about 3000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • the detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1:1.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N′-disuccinic acid
  • alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof Especially preferred is ethylenediamine-N,N′-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • the detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01% to 5%, more preferably from 0.1% to 1% by weight of the compositions.
  • a crystal growth inhibitor component preferably an organodiphosphonic acid component
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C 1 -C 4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1-hydroxy-1,1-diphosphonic acid
  • Another optional ingredient useful in the compositions is one or more enzymes.
  • Preferred enzymatic materials include the commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is described in Granted European Patent, EP-B-0218272.
  • An especially preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza , as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.
  • Preferred enzyme-containing compositions herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • Organic polymeric compounds may be added as preferred separate components of the compositions in accord with the invention.
  • organic polymeric compounds may find use as organic binders in the process aspect of the invention as described hereinbefore.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • such salts are polyacrylates of average molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a average molecular weight of from 20,000 to 100,000.
  • Preferred commercially available acrylic acid containing polymers having a average molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula —[CR 2 —CR 1 (CO—O—R 3 )]— wherein at least one of the substituents R 1 , R 2 or R 3 , preferably R 1 or R 2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R 1 or R 2 can be a hydrogen and R 3 can be a hydrogen or alkali metal salt.
  • the most preferred copolymer of this type has a average molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • compositions of the invention may contain a lime soap dispersant compound, preferably present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
  • Preferred lime soap disperant compounds are disclosed in PCT Application No. WO93/08877 (attorney's docket no. CM466M).
  • compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds.
  • Preferred suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 (attorney's docket no. CM465M) and copending European Application No. 93870132.3 (attorney's docket no. CM562F).
  • compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • compositions may contain corrosion inhibitors such as benzotriazole and paraffin. Suitable corrosion inhibitors are described in PCT Application No. WO94/07981 and copending European Application No. EP 93202095.1.
  • the bulk density of granular detergent compositions in accordance with the present invention is typically of at least 650 g/liter, more usually at least 700 g/liter and more preferably from 800 g/liter to 1200 g/liter.
  • the particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4 mm in diameter and not more than 5% of particles are less than 0.15 mm in diameter.
  • Any suitable methods for washing or cleaning soiled tableware, including soiled patterned glassware and silverware, are envisaged including machine dishwashing methods.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention.
  • an effective amount of the machine dishwashing composition it is meant from 8 g to 60 g of product dissolved or dispersed in a wash solution of volume from 3 to 10 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • Protease Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S (approx 2% enzyme activity).
  • Amylase Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S (approx 0.9% enzyme activity)
  • BSA Amylolytic enzyme sold under the tradename LE17 by Novo Industries A/S (approx 1% enzyme activity) Sulphate Anhydrous sodium sulphate. pH Measured as a 1% solution in distilled water at 20° C.
  • a green silicate speckle was made in accord with the invention as follows:
  • An aqueous mixture of organic binder and two dyestuffs was made up by adding with continuous mixing 2.44 kg of E104—quinoline yellow, 0.16 kg of E131—patent blue V and 10.53 kg of 480N to 100 kg of water. Continuous agitation of the mixture is necessary to keep the dyesuffs evenly dispersed in the suspension.
  • a second batch of silicate speckle was made up using identical process steps to Example 1, other than that Pigment Green 7 was used instead of E104 and E131 to give a speckle, hereinafter ‘green speckle 2’, having the composition:
  • compositions A and D are comparative compositions
  • compositions B, C and E to G are in accord with the invention.
  • compositions B and E in accord with the invention was compared to that of comparative Compositions A and D using the following three hundred-cycle test procedure.
  • a set of twelve household glasses was placed in the upper rack of a Bosch Siemens SMS6032 (tradename) machine dishwasher.
  • the 65° C. wash setting was selected, the wash process comprising main wash and rinse cycles.
  • 20 grams of compositions A and B, and 40 grams of compositions D and E was employed respectively, for each complete wash process.
  • 54 g of a representative food soil was added to each machine.
  • the feed water hardness was 18° German Hardness (321 ppm CaCO 3 equivalent).
  • Dishwasher salt was employed to reduce the in wash water hardness to about 2° German Hardness (36 ppm CaCNa 3 equivalent).
  • the set of twelve glasses was washed three hundred times, with a period of cooling, in which the dishwsaher door was left open, being allowed between each complete wash cycle.
  • Results were as follows: (average of the 2 gradings from the panellists)
  • compositions are made up having identical compositions to those of B, C and E to G of Example 3, other than that the ‘green speckle 1’ is replaced by the ‘green speckle 2’ of Example 2 at identical levels of incorporation.

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US6645471B2 (en) * 2001-11-08 2003-11-11 J. M. Huber Corporation Composite abrasive material for oral compositions, and methods of making and using same
US20040147427A1 (en) * 2002-11-14 2004-07-29 The Procter & Gamble Company Rinse aid containing encapsulated glasscare active salt
US20110009304A1 (en) * 2009-07-09 2011-01-13 Nigel Patrick Somerville-Roberts Compositions containing bleach co-particles
US20110009305A1 (en) * 2009-07-09 2011-01-13 Nigel Patrick Somerville Roberts Layered Particles and Compositions Comprising Same
US20110166370A1 (en) * 2010-01-12 2011-07-07 Charles Winston Saunders Scattered Branched-Chain Fatty Acids And Biological Production Thereof
US20110294716A1 (en) * 2010-05-28 2011-12-01 Steven Spanhove Colored Speckles For Use In Granular Detergents
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates

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DE19641708A1 (de) 1996-10-10 1998-04-16 Clariant Gmbh Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
DE19821695A1 (de) * 1998-05-14 1999-11-25 Henkel Kgaa Gefärbte maschinelle Geschirrspülmittel
GB2343456A (en) * 1998-11-06 2000-05-10 Procter & Gamble Speckle particles and compositions containing the speckle particles
DE19855676A1 (de) * 1998-12-02 2000-06-08 Henkel Kgaa Wasch- und Reinigungsmitteladditiv und Verfahren zu dessen Herstellung
GB2348884A (en) * 1999-04-13 2000-10-18 Procter & Gamble Light reflecting particles
DE19943254A1 (de) 1999-09-10 2001-03-15 Clariant Gmbh Bleichaktive Metallkomplexe
DE19960744A1 (de) * 1999-12-16 2001-07-05 Clariant Gmbh Granulares Alkalischichtsilicat-Compound
WO2003018740A1 (en) * 2001-08-20 2003-03-06 Unilever Plc Photobleach speckle and laundry detergent compositions containing it
GB0120160D0 (en) 2001-08-20 2001-10-10 Unilever Plc Photobleach speckle and laundry detergent compositions containing it
GB2415695A (en) * 2004-07-02 2006-01-04 Reckitt Benckiser Nv Detergent composition comprising a chelating agent
CN103380107B (zh) 2011-02-17 2015-06-10 宝洁公司 生物基直链烷基苯基磺酸盐

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US6645471B2 (en) * 2001-11-08 2003-11-11 J. M. Huber Corporation Composite abrasive material for oral compositions, and methods of making and using same
US20040147427A1 (en) * 2002-11-14 2004-07-29 The Procter & Gamble Company Rinse aid containing encapsulated glasscare active salt
US20110009304A1 (en) * 2009-07-09 2011-01-13 Nigel Patrick Somerville-Roberts Compositions containing bleach co-particles
US20110009305A1 (en) * 2009-07-09 2011-01-13 Nigel Patrick Somerville Roberts Layered Particles and Compositions Comprising Same
US20110166370A1 (en) * 2010-01-12 2011-07-07 Charles Winston Saunders Scattered Branched-Chain Fatty Acids And Biological Production Thereof
US20110171155A1 (en) * 2010-01-12 2011-07-14 Thomas Walter Federle Intermediates And Surfactants useful In Household Cleaning And Personal Care Compositions, And Methods Of Making The Same
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US20110294716A1 (en) * 2010-05-28 2011-12-01 Steven Spanhove Colored Speckles For Use In Granular Detergents
US8470760B2 (en) * 2010-05-28 2013-06-25 Milliken 7 Company Colored speckles for use in granular detergents
US8921301B2 (en) * 2010-05-28 2014-12-30 Milliken & Company Colored speckles for use in granular detergents
US11649417B2 (en) 2010-05-28 2023-05-16 Milliken & Company Colored speckles for use in granular detergents
US9193937B2 (en) 2011-02-17 2015-11-24 The Procter & Gamble Company Mixtures of C10-C13 alkylphenyl sulfonates

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